The following description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art, or relevant, to the presently described or claimed invention, or that any publication or document that is specifically or implicitly identified is prior art or a reference that may be used in evaluating patentability.
A fire retardant is a substance that helps to delay or prevent combustion. See Horrocks, A. R., Fire Retardant Materials (2001). Fire retardant clothing, for example, is widely used to protect persons who are exposed to fire, particularly suddenly occurring and fast burning conflagrations. These include persons in diverse fields such as race car drivers, military personnel and fire fighters, each of which may be exposed to deadly fires and extremely dangerous incendiary conditions without notice. For such persons, the primary line of defense against severe burns and even death is the protective clothing worn over some or all of the body.
Materials such as carbon fiber materials and aramid fiber materials have been used to form fire retardant materials for the manufacture of clothing. Carbon fibers are typically in the form of long bundles of linked graphite plates that form a crystal structure lying parallel to the fiber axis. Carbon fibers are anisotropic and their elastic modulus is higher in the direction of the axis than it is in other directions. In other words, the individual fibers can withstand pulling, i.e., they can stretch before breaking, in the axial direction to a greater extent than they can withstand bending at an angle to the axis or lateral stretching. Most carbon fiber materials are made from thousands of individual filaments and include thousands of fibers.
Carbon fiber materials have advantageous mechanical, physical and chemical properties. In addition to being nonflammable, they are light, stiff and strong. The strength of a carbon fiber is comparable to that of steels and the stiffness of carbon fibers is generally greater than metal, ceramic or polymer-based materials. Carbon fibers have other desirable properties such as excellent corrosion and fatigue resistance and dimensional stability. Carbon fibers and their composites are therefore well suited for applications in which chemical inertness, strength, stiffness, lightness, and fatigue resistance are important requirements. For example, in the aerospace and defense industries, materials made of carbon fibers have been increasingly used both in the interior of aircrafts as flame resistant materials and as critical structural components to increase fuel efficiency and enhance structural strength.
Carbon fibers may be produced from a variety of precursor materials. Among these precursor materials are polyacrylonitrile (PAN), petroleum or coal tar pitch and certain phenolic fibers. Cellulosic fibers such as rayon and cotton may also be used as additives. Different precursor materials produce carbon fibers with different morphologies and different specific characteristics. PAN-based carbon fiber materials exhibit superior tensile strength, are comparatively low in cost, and are well suited for use in the construction of consumer goods such as sporting goods and high-performance apparel.
Various methods are known for producing carbon fibers from various precursor materials. Such methods include pyrolytic processes and pyrolysis. It is well established that the mechanical properties of carbon fibers are improved by increasing their crystallinity and the molecular order within the fiber. One way to increase crystallinity and structural order is through a process of stabilization and carbonization through tension. One common pyrolysis reaction is an oxidative stabilization process in which a carbon fiber is treated at about 200-300° C. under tension in an oxidizing environment. During the process, oxygen, nitrogen and/or hydrogen is removed from the fiber, resulting in an increase of carbon content in the fiber. In addition to preventing fiber shrinkage, the tension applied during this process maintains the molecular orientation and order of the fiber, which in turn increases the tensile strength of the stabilized fiber.
During pyrolysis of PAN, the oxidation and stabilization induces intramolecular cyclization of the oriented molecules with the release of most of the hydrogen and part of the nitrogen from the fibers. The resulting PAN polymers are called “oxidized PAN” and oxidized PAN typically has a carbon content of about 55-68% and a density of about 1.30 to 1.50 g/cm3. Oxidized PAN fibers have several advantages as flame resistant materials. Oxidized PAN fibers exhibit excellent heat insulation properties and low thermal conductivity. Oxidized PAN fibers also have a high limiting oxygen index (LOI), typically between 40-60% oxygen making them more flame resistant than many other organic fibers. Moreover, textiles that include strands of oxidized PAN fibers, unlike other flame resistant organic fibers, retain their appearance and textile characteristics after open flame exposure. Oxidized PAN fibers are electrically nonconductive and function as effective electrical insulators even after exposure to heat and open flames. Oxidized PAN fibers also exhibit excellent chemical resistance to organic solvents and most acids and bases. Moreover, oxidized PAN fiber strands are softer, more pliable and malleable than strands of pure carbon fibers. As such, oxidized PAN fiber strands are well suited for use in composite heat resistant thermal insulations and textiles for high technology applications, and have been used in composite fire blocking fabrics for seating in the aerospace and automobile industries and in the manufacture of composite fire retardant and protective clothing for people exposed to the danger of an open flame.
Currently, there are at least three types of oxidized PAN materials available commercially: staple fibers, large filament tow materials, and small filament tow materials. In using these materials in the production of composite industrial and consumer products, the staple fibers and large filament tow materials are often spun into yarn using complex, multi-step processes that commonly include, for example, the addition of strengthening fibers to the carbon fiber material precursor, or the addition of laminate coatings to fabrics that they are used to prepare.
For staple fibers, relatively short natural or synthetic fibers, the first step in the production of yarn is “carding”, in which the fibers are opened and combed over cylinders that contain extremely fine wires or aligned teeth. The fibers are then aligned in one direction to form a large loosely assembled but not twisted continuous strands of fibers known as “sliver”. Several strands of sliver are then drawn multiple times onto drawing frames to further align the fibers to improve uniformity as well as to reduce the diameter of the sliver. The drawn sliver is then fed into a roving frame to produce “roving” by further reducing the diameter and imparting a slight false twist. Finally, the roving is fed into a spinning (i.e., winding and/or twisting) frame where it is spun into yarn.
For large filament tow, the first step is different, and consists of a stretch-breaking process in which the large tow is broken into multiple fragments and aligned into sliver. The sliver is then further processed as described above. These processes are laborious, inefficient and costly, require as many as 6 or 8-12 separate steps and often require the use of more than one type of apparatus.
It would be desirable to provide an economical process for converting oxidized PAN materials or other starting materials into yarn using a reduced and minimum number of operations. It would be further desirable to provide a process for converting oxidized PAN materials or other starting materials into yarn using a single apparatus.
Oxidized PAN materials provide superior fire retardant and heat resistant qualities, i.e., a high LOI and superior Thermal Protective Performance, TPP, but when they are formed according to conventional methods, the strands formed from oxidized PAN carbon fibers are typically brittle, weak and prone to abrasion and cutting. Yarns formed from pure oxidized PAN using conventional methods exhibit undesirably low cut resistance, abrasion resistance and tensile strength and do not include sufficient tensile strength to be knit or woven into fabrics. As such, fabrics made from oxidized PAN carbon fiber strands using conventional methods typically include the fire retardant and heat resistant oxidized PAN strands in combination with one or more high strength or strengthening filaments/fibers. Aramid fiber is an example of such a strengthening filament. The strengthening filaments/fibers in combination with the oxidized PAN produces a fibrous blend having improved tensile strength, cut resistance and durability but the additives, i.e., the strengthening fibers, compromise the flame retarding and heat resisting properties of the fabric.
It would be desirable to produce a yarn and textile and other materials that are composed entirely of oxidized polyacrylonitrile fibers or carbonized polyacrylonitrile fibers yet exhibit sufficient tensile strength to be knittable. It would also be desirable to manufacture an intermediate product that may be used to produce such yarns and textile and other materials.